Black-dyeing inks and their use

ABSTRACT

Black-dyeing aqueous inks having good black shades without a shade change in artificial light and outstanding lightfastness comprising 20 to 95% by weight of at least one dye (A), together with 5 to 80% by weight of at least one dye chosen from the group consisting of (B) and (C), based on the total weight of the dyes (A), (B) and (C) in the ink, and 1 to 40% by weight of a water-miscible organic solvent, based on the total weight of the ink, the dye (A) containing, as the colouring part of the molecule, one or more radicals of the formula (I), (II), (III) or (IV)                    
     the dye (B) containing, as the colouring part of the molecule, one or more mono- or disazo radicals containing sulfo groups or one or more radicals of the formula (V), (VI), (VII) or (VIII)                    
     and the dye (C) containing, as the colouring part of the molecule, one or more mono- or disazo radicals containing sulfo groups or one or more radicals of the formulae (V), (VI), (VII) or (VII) and one or more radicals of the formulae (I), (II), (III) or (IV), in which the substituents are as defined herein.

The present invention relates to black-dyeing inks based on navy bluecopper complex azo or copper complex formazan dyes, black-dyeingmixtures based on such dyes and novel dyes.

The inks on which the present invention is based are particularlysuitable for printing paper, preferably by the ink-jet printing process,and for dyeing or printing fibre materials which contain nitrogen orhydroxyl groups, and give dyeings or prints which are distinguished by ahigh fastness to light.

The present invention therefore relates to black-dyeing aqueous inkscomprising 20 to 95% by weight of at least one dye (A), together with 5to 80% by weight of at least one dye chosen from the group consisting of(B) and (C), based on the total weight of the dyes (A), (B) and (C) inthe ink, and 1 to 40% by weight of a water-miscible organic solvent,based on the total weight of the ink, the dye (A) containing, as thecolouring part of the molecule, one or more radicals of the formula (I),(II), (III) or (IV)

the dye (B) containing, as the colouring part of the molecule, one ormore mono- or disazo radicals containing sulfo groups or one or moreradicals of the formula (V), (VI), (VII) or (VIII)

and the dye (C) containing, as the colouring part of the molecule, oneor more mono- or disazo radicals containing sulfo groups or one or moreradicals of the abovementioned formula (V), (VI), (VII) or (VII) and oneor more radicals of the abovementioned formula (I), (II), (III) or (IV),in which

(G)₀₋₂ is 0 to 2 identical or different substituents from the groupconsisting of substituted or unsubstituted amino, hydroxyl and nitro,

L is substituted or unsubstituted amino,

R is halogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, hydroxyl,carboxyl, nitro or cyano,

(V)₀₋₂ is 0 to 2 identical or different substituents from the groupconsisting of halogen, C₁-C₄alkyl, C₁-C₄alkoxy, β-sulfatoethylsulfonyland sulfo,

(W)₀₋₁ is an N-acyl radical, if any,

n is the number 0, 1, 2 or 3,

m is the number 1, 2 or 3 and

r and q are the number O or 1.

C₁-C₄alkyl R and V is, for example, methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl,and in particular methyl.

C₁-C₄alkoxy R and V is, for example, methoxy, ethoxy, propoxy,isopropoxy, butoxy or isobutoxy, preferably methoxy or ethoxy, and inparticular methoxy.

Halogen R and V is, for example, fluorine, chlorine or bromine,preferably chlorine or bromine, and in particular chlorine.

C₂-C₄alkanoylamino R is, for example, acetylamino or propionylamino, inparticular acetylamino.

R is preferably C₁-C₄alkyl, C₁-C₄alkoxy, hydroxyl, carboxyl, nitro orcyano, in particular C₁-C₄alkyl, C₁-C₄alkoxy, hydroxyl or carboxyl, andespecially carboxyl.

V is preferably halogen, βsulfatoethylsulfonyl or sulfo, in particularsulfo.

Substituted or unsubstituted amino G and L is, for example, amino,N-mono- or N,N-di- C₁-C₄alkylamino which are unsubstituted orsubstituted in the alkyl moiety by C₁-C₄alkoxy, hydroxyl, sulfato orsulfo, or phenylamino or N-C₁-C₄alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl ring by C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, carboxyl or halogen, inparticular amino or phenylamino.

An N-acyl radical W is, for example, C₂-C₄alkanoylamino, for exampleacetylamino or propionylamino, benzoylamino which is unsubstituted orsubstituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen orsulfo, or a radical of the formula

in which T₁ and T₂ independently of one another are fluorine orchlorine, C₁-C₄alkylthio which is unsubstituted or substituted in thealkyl moiety by hydroxyl, sulfato, sulfo or carboxyl, hydroxyl, amino,N-mono- or N,N-di-C₁-C₄alkylamino which is unsubstituted or substitutedin the alkyl moiety by hydroxyl, carboxyl, C₁-C₄alkoxy, sulfato orsulfo, morpholino, phenylamino or N-C₁-C₄alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl ring by sulfo, carboxyl,acetylamino, chlorine, methyl or methoxy and in which the alkyl isunsubstituted or substituted by hydroxyl, sulfo or sulfato, ornaphthylamino which is unsubstituted or substituted by 1 to 3 sulfogroups.

q is preferably the number 1.

m is preferably the number 2 or 3, in particular 2.

If R is carboxyl, the sum of m+n is preferably 3 or 4, and in particular3.

Inks according to the invention which are preferred are those whichcontain a radical of the formula (IV) in which

q is the number 1,

n is the number 0 and

m is the number 2 or 3.

The sulfo groups of the dyes (A), (B) and (C) in the inks according tothe invention are either in the form of the free sulfonic acid or,preferably, in the salt form thereof, for example as the sodium,lithium, potassium or ammonium salt or as the salt of an organic amine,for example as the triethanolammonium salt.

The dyes (A), (B) and (C) in the inks according to the invention containno further colouring molecular moieties in addition to the colouringmolecular moieties mentioned.

The dye (A) in the inks according to the invention preferably contains,as the colouring molecular moiety (chromophore), one or two radicals ofthe formula (I), (II), (III) or (IV).

If the dye (A) contains a radical of the formula (I), (II), (III) or(IV), a non-chromophoric radical is bonded to this radical via the freevalency drawn in the formulae (I), (II), (III) and (IV).

Examples of a non-chromophoric radical are the following:

C₂-C₆alkanoylamino which is unsubstituted or substituted in the alkylmoiety by hydroxyl, sulfo, carboxyl or C₁-C₄alkoxy, which can in itsturn be substituted in the alkyl moiety by carboxyl, for exampleacetylamino, hydroxyacetylamino, methoxyacetylamino,carboxymethylenoxyacetylamino, propionylamino orβ-carboxypropionylamino; N-C₁-C₄alkylamino which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl, sulfo, carboxyl orC₁-C₄alkoxy, for example 3-sulfopropylamino or 4-sulfobutylamino;benzoylamino which is unsubstituted or substituted in the phenyl moietyby hydroxyl, sulfo, halogen, C₁-C₄alkyl or C₁-C₄alkoxy;C₂-C₆alkoxycarbonylamino which is unsubstituted or substituted in thealkyl moiety by hydroxyl, C₁-C₄alkyl or C₁-C₄alkoxy;phenoxycarbonylamino which is unsubstituted or substituted in the phenylmoiety by hydroxyl, C₁-C₄alkyl or C₁-C₄alkoxy; phenylsulfonylamino whichis unsubstituted or substituted in the phenyl moiety by C₁-C₄alkyl orC₂-C₄alkanoylamino, or C₁-C₄alkylsulfonylamino, for example methyl- orethylsulfonylamino, or a radical of the formula

 in which T₃ and T₄ independently of one another are a substituent whichis not fibre-reacted, for example C₁-C₄alkoxy, C₁-C₄alkylthio which isunsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato,sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylaminowhich is unsubstituted or substituted in the alkyl moiety by hydroxyl,carboxyl, C₁-C₄alkoxy, sulfato or sulfo, morpholino, phenylamino orN-C₁-C₄alkyl-N-phenylamino, which are unsubstituted or substituted inthe phenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl ormethoxy, and in which the alkyl is unsubstituted or substituted byhydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted orsubstituted by 1 to 3 sulfo groups.

Non-chromophoric radicals which are bonded via the free valency in theformula (I), (II), (III) or (IV) are also fibre-reactive radicals.

Fibre-reactive radicals are, for example, an alkanoyl or alkylsulfonylradical substituted by an atom which can be split off or a group whichcan be split off, an alkenoyl or alkenesulfonyl radical which isunsubstituted or substituted by an atom which can be split off or agroup which can be split off, or an alkenoyl or alkenesulfonyl radicalwhich contains a vinyl group. The alkanoyl, alkylsulfonyl andalkenesulfonyl radicals mentioned as a rule contain 2 to 8 carbon atomsand the alkenoyl radicals as a rule contain 3 to 8 carbon atoms. Theseradicals are also radicals which contain carbo- or heterocyclic 4-, 5-or 6-membered rings and are substituted by an atom which can be splitoff or a group which can be split off. Heterocyclic radicals are, forexample, those which contain at least one substituent which can be splitoff bonded to a heterocyclic radical; inter alia, those which contain atleast one reactive substituent bonded to a 5- or 6-membered heterocyclicring, such as to a monoazine, diazine, triazine, pyridine, pyrimidine,pyridazine, pyrazine, thiazine, oxazine or asymmetric or symmetrictriazine ring, or to such a ring system which has one or more fused-onaromatic rings, such as a quinoline, phthalazine, quinazoline,quinoxaline, acridine, phenazine and phenanthridine ring system.

Atoms which can be split off and groups which can be split off are, inaddition to others, for example, halogen, such as fluorine, chlorine orbromine, ammonium, including hydrozinium, sulfato, thiosulfato,phosphato, acetoxy, propionoxy, azido, carboxypyridinium or thiocyanato.

The fibre-reactive radical and the chromophore of the formula (I), (II),(III) or (IV) can be bonded to one another by a bridge member. Bridgemembers are, in addition to the direct bond or, for example, an aminogroup, the most diverse radicals. The bridge member is, for example, analiphatic, aromatic or heterocyclic radical; the bridge member canfurthermore also be composed of different such radicals. The bridgemember as a rule contains at least one functional group, for example thecarbonyl, sulfonyl, carbonylamino, sulfonylamino or the amino group, itbeing possible for the amino group to be further substituted byC₁-C₄alkyl which is unsubstituted or substituted by halogen, hydroxyl,cyano, C₁-C₄alkoxy, C₁-C₄alkoxycarbonyl, carboxyl, sulfamoyl, sulfo orsulfato. An aliphatic radical is, for example, an alkylene radicalhaving 1 to 7 carbon atoms or branched isomers thereof. The carbon chainof the alkylene radical can be interrupted by a heteroatom, for examplean oxygen atom. An aromatic radical is, for example, a phenyleneradical, which can be substituted by C₁-C₄alkyl, for example methyl orethyl, C₁-C₄alkoxy, for example methoxy or ethoxy, halogen, for examplefluorine, bromine or, in particular, chlorine, carboxyl or sulfo, and aheterocyclic radical is, for example, a piperazine or a triazineradical, it being possible for the triazine radical to contain asubstituent which can be split off, for example fluorine or chlorine.

Such fibre-reactive radicals are known per se and a large number aredescribed, for example, in Venkataraman “The Chemistry of SyntheticDyes” Volume 6, Pages 1-209, Academic Press, New York, London 1972 or inU.S. Pat. No. 5,684,138.

The dyes (A) which comprise a chromophore of the formula (I), (II),(III) or (IV) are known or can be prepared analogously to known dyes.

Suitable dyes (A) which comprise a chromophore of the formula (IV) are,for example, C.I. Reactive Blue 52, 70, 83, 84, 104, 157, 160, 182, 202,209, 212, 218, 220, 221, 226, 228 and 232 and the dyes of the formulae(IV.1), (IV.2), (IV.3), (IV.4), (IV.5), (IV.6), (IV.7) and (IV.8)

preferably C.I. Reactive Blue 52 and 182 and the dyes of the formulae(IV.1), (IV.2), (IV.3), (IV.4), (IV.5), (IV.6), (IV.7) and (IV.8), andin particular the dyes of the formulae (IV.1), (IV.2), (IV.3), (IV.4),(IV.5), (IV.6), (IV.7) and (IV.8).

Suitable dyes which comprise a chromophore of the formula (IV) andcontain a fibre-reactive radical are furthermore described, for example,in GB-A-2 148 921, U.S. Pat. No. 4,994,562, U.S. Pat. No. 5,021,557,U.S. Pat. No. 5,023,274, U.S. Pat. No. 5,076,811, U.S. Pat. No.5,112,958 and U.S. Pat. No. 5,371,200.

If the dye (A) contains two radicals of the formula (I), (II), (III) or(IV), these radicals are bonded to one another by a bridge member, ineach case via the free valency in the formulae (I), (II), (III) and(IV). Bridge members are the most diverse radicals. The bridge memberis, for example, an aliphatic, aromatic or heterocyclic radical; thebridge member can furthermore also be composed of different suchradicals. The bridge member as a rule contains at least two functionalgroups, for example the carbonyl, sulfonyl, carbonylamino, sulfonylaminoor the amino group, it being possible for the amino group to be furthersubstituted by C₁-C₄alkyl which is unsubstituted or substituted byhalogen, hydroxyl, cyano, C₁-C₄alkoxy, C₁-C₄alkoxycarbonyl, carboxyl,sulfamoyl, sulfo or sulfato. An aliphatic radical is, for example, analkylene radical having 1 to 10 carbon atoms or branched isomersthereof. The carbon chain of the alkylene radical can be interrupted bya heteroatom, for example an oxygen atom. The term aliphatic radicalalso includes cycloaliphatic radicals. An aromatic radical is, forexample, a naphthylene radical, the radical of a diphenyl or stilbene,or, in particular, a phenylene radical, which can be substituted byC₁-C₄alkyl, for example methyl or ethyl, C₁-C₄alkoxy, for examplemethoxy or ethoxy, halogen, for example fluorine, bromine or, inparticular, chlorine, carboxyl or sulfo, and a heterocyclic radical is,for example, a triazine radical.

The dyes (A) which comprise two chromophore radicals of the formula (I),(II), (III) or (IV) bonded to one another via a bridge member are knownor can be prepared analogously to known dyes. A suitable dye is, forexample, the dye of the formula (IV.9)

Suitable dyes (A) which comporise two chromophore radicals of theformula (IV) bonded to one another via a bridge member are furthermoredescribed, for example, in GB-A-1 389 053, GB-A-2 148 921, U.S. Pat. No.5,232,462, U.S. Pat. No. 5,410,041 and U.S. Pat. No. 5,684,138.

The chromophore of the formula (I), (II) or (III) contained in the dye(A) is preferably one or two radicals of the formula (I.1), (I.2),(I.3), (I.4), (I.5), (II.1), (II.2), (II.3) or (III.1)

The chromophore contained in the dye (C) is preferably a mono- or disazoradical containing sulfo groups or a radical of the formula (V), (VI),(VII) or (VII) and a radical of the formula (I), (II), (III) or (IV).

The mono- or disazo radicals and the radicals of the formulae (V), (VI),(VII) and (VII) on which the dyes (B) and (C) of the inks according tothe invention are based are, for example, yellow-, orange-, red- orclaret- to violet-colouring dye radicals.

Suitable dye radicals of the formula (V), (VI), (VII) and (VII) are, forexample, those of the formulae (V.1), (V.2), (V.3), (V.4), (V.5), (V.6),(V.7), (VI.1), (VII.1), (VIII.1), (VIII.2) and (VIII.3)

The chromophore of the formula (IV) contained in the dye (A) ispreferably one or two radicals of the formula (IVa), (IVb) or (IVc)

in particular of the formula (IVb) or (IVc).

The chromophore contained in the dye (B) is preferably one or two mono-or disazo radicals containing sulfo groups or one or two radicals of theformula (V), (VI), (VII) or (VIII).

Examples of substituents in the mono- or disazo radical are thefollowing:

alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl,isopropyl or butyl, it being possible for the alkyl radicals to befurther substituted, for example by hydroxyl, sulfo or sulfato; alkoxygroups having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy,isopropoxy or butoxy, it being possible for the alkyl radicals to befurther substituted, for example by hydroxyl, sulfo or sulfato; phenylwhich is unsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,halogen, carboxyl or sulfo; acylamino groups having 1 to 8 carbon atoms,in particular such alkanoylamino groups, for example acetylamino orpropionylamino; benzoylamino which is unsubstituted or substituted inthe phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen or sulfo;phenylamino which is unsubstituted or substituted in the phenyl ring byC₁-C₄alkyl, C₁-C₄alkoxy, halogen or sulfo; N,N-di-β-hydroxyethylamino;N,N-di-β-sulfatoethylamino; sulfobenzylamino; N,N-disulfobenzylamino;alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy radical, such asmethoxycarbonyl or ethoxycarbonyl; alkylsulfonyl having 1 to 4 carbonatoms, such as methylsulfonyl or ethylsulfonyl; trifluoromethyl; nitro;amino; cyano; halogen, such as fluorine, chlorine or bromine; carbamoyl;N-alkylcarbamoyl having 1 to 4 carbon atoms in the alkyl radical, suchas N-methylcarbamoyl or N-ethylcarbamoyl; sulfamoyl; N-mono- orN,N-dialkylsulfamoyl having in each case 1 to 4 carbon atoms, such asN-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl,N-isopropylsulfamoyl or N-butylsulfamoyl, it being possible for thealkyl radicals to be further substituted, for example by hydroxyl orsulfo; N-(β-hydroxyethyl)-sulfamoyl; N,N-di-(β-hydroxyethyl)-sulfamoyl;N-phenylsulfamoyl which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxyl or sulfo; ureido; hydroxyl; carboxyl;sulfomethyl or sulfo, and the fibre-reactive radicals described above.

The mono- or disazo radicals containing sulfo groups in the dyes (B) and(C) of the inks according to the invention are preferably those of theformula (2) or (3)

D—N═N—(M—N═N)_(u)—K—  (2)

or

—D—N═N—(M—N═N)_(u)—K  (3),

in which D is the radical of a diazo component of the benzene ornaphthalene series, M is the radical of a middle component of thebenzene or naphthalene series, K is the radical of a coupling componentof the benzene, naphthalene, pyrazolone, 6-hydroxypyrid-2-one oracetoacetic acid arylamide series and u is the number 0 or 1, where D, Mand K can carry substituents customary in azo dyes, for exampleC₁-C₄alkyl or C₁-C₄alkoxy which are unsubstituted or further substitutedby hydroxyl, sulfo or sulfato, halogen, carboxyl, sulfo, nitro, cyano,trifluoromethyl, sulfamoyl, carbamoyl, amino, ureido, hydroxyl,sulfomethyl, C₂-C₄alkanoylamino, benzoylamino which is unsubstituted orsubstituted in the phenyl ring by C₁-C₄alkyl, C₁-C₄alkoxy, halogen orsulfo, phenyl which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, halogen, carboxyl or sulfo, and fibre-reactive radicals.

If u is the number 1, D, M and K are preferably radicals of a diazo,middle and coupling component of the benzene or naphthalene series, andin particular of the benzene series.

A radical of the formula (2) or (3) in the dye (B) has bonded to it, viathe free valency drawn in the formula (2) or (3), a non-chromophoricsubstituent, for example one of the substituents mentioned above formono- or disazo radicals, or a radical of the formula

in which T₃ and T₄ independently of one another are a substituent whichis not fibre-reactive, for example C₁-C₄alkoxy, C₁-C₄alkylthio which isunsubstituted or substituted in the alkyl moiety by hydroxyl, sulfato,sulfo or carboxyl, hydroxyl, amino, N-mono- or N,N-di-C₁-C₄alkylaminowhich are unsubstituted or substituted in the alky moiety by hydroxyl,carboxyl, C₁-C₄alkoxy, sulfato or sulfo, morpholino, phenylamino orN-C₁-C₄alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl ring by sulfo, carboxyl, acetylamino, chlorine, methyl ormethoxy, and in which the alkyl is unsubstituted or substituted byhydroxyl, sulfo or sulfato, or naphthylamino which is unsubstituted orsubstituted by 1 to 3 sulfo groups.

The radicals mentioned can also satisfy the free valency of the dye (B)which comprises a chromophore radical of the formula (V), (VI), (VII) or(VII).

The dyes (B) which comprise a chromophore of the formula (2), (3), (V),(VI), (VII) or (VII) are known or can be prepared analogously to knowndyes.

Suitable dyes (B) which comprise a chromophore of the formula (2) are,for example, the dyes of the formulae (2.1), (2.2), (2,3) and (2.4)

Two radicals of the formula (2), (3), (V), (VI), (VII) or (VIII),contained in the dye (B) are bonded to one another by a bridge member,in each case via the free valency. Bridge members are, for example,those radicals which have already been described above in connectionwith the dye (A) containing two radicals of the formula (I), (II), (III)or (IV).

The dyes (B) which comprise two chromophore radicals of the formula (2),(3), (V), (VI), (VII) or (VIII) bonded to one another via a bridgemember are known or can be prepared analogously to known dyes.

Suitable dyes (B) which comprise two chromophore radicals of the formula(2) bonded to one another via a bridge member are, for example, the dyesof the formulae (2.5), (2.6) and (2.7)

The dye radicals in the dye (C) are bonded to one another via a bridgemember, in each case via the free valency in the formula (I), (II),(III) or (IV) and the formula (2), (3), (V), (VI), (VII) or (VIII).Bridge members are, for example, those radicals which have already beendescribed above in connection with the dye (A) containing two radicalsof the formula (I), (II), (III) or (IV).

The dyes (C) on which the inks according to the invention are based areknown in some cases or can be prepared analogously to known dyes. Thepresent invention also relates to the novel dyes (C) on which the inksaccording to the invention are based.

Suitable dyes (C) and dyes (B) which comprise two chromophore radicalsbonded to one another via a bridge member are furthermore described, forexample, in U.S. Pat. No. 5,232,462, U.S. Pat. No. 5,243,033, U.S. Pat.No. 5,410,041 and U.S. Pat. No. 5,684,138.

The radicals of the formulae (2) and (3) each contain at least one sulfogroup, preferably 1 to 4 sulfo groups, in particular 1 to 3 sulfogroups, and especially 2 sulfo groups.

The dye (C) preferably contains, as the chromophore, a radical of theformula (I), (II), (III), (IVa), (IVb) or (IVc), in particular (I.1),(I.2), (I.3), (I.4), (I.5), (II.1), (II.2), (II.3), (II.1), (III.1),(IVb) or (IVc).

The radicals of the formulae (2) and (3) are preferably radicals of theformula (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j),(4k), (41), (4m), (4n), (4o), (4p), (4q) or (4r)

in which (R₁)₀₋₃ is 0 to 3 identical or different substituents from thegroup consisting of C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino,halogen, carboxyl and sulfo and Z is vinyl or a radical —CH₂—CH₂—U and Uis a leaving group,

in which (R₁)₀₋₃ is as defined above,

in which (R₁)₀₋₃ is as defined above,

in which (R₂)₀₋₄ is 0 to 4 identical or different substituents from thegroup consisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxy which is unsubstituted or substitutedby hydroxyl or C₁-C₄alkoxy, amino, C₂-C₄alkanoylamino, ureido, hydroxyl,carboxyl, sulfomethyl, C₁-C₄alkylsulfonylamino and sulfo and Z is asdefined above,

in which R₃ is C₂-C₄alkanoyl or benzoyl,

in which R₃ is as defined above,

in which (R₄)₀₋₃ is 0 to 3 identical or different substituents from thegroup consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl andsulfo,

in which (R₄)₀₋₃ is as defined above,

in which R₅ and R₇ independently of one another are hydrogen, C₁-C₄alkylor phenyl, and R₆ is hydrogen, cyano, carbamoyl or sulfomethyl,

in which (R₈)₀₋₂ is 0 to 2 identical or different substituents from thegroup consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl andsulfo; and Z is as defined above,

in which (R₉)₀₋₂ is 0 to 2 identical or different substituents from thegroup consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl andsulfo; and Z is as defined above,

in which

(R₁)₀₋₃, (R₂)₀₋₃, (R₄)₀₋₃ and Z are each as defined above and (R₁′)₀₋₃is 0 to 3 identical or different substituents from the group consistingof C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl and sulfo.

C₁-C₄alkyl R₁, R₁′, R₂, R₄, R₅, R₇, R₈ and R₉ independently of oneanother are, for example, methyl, ethyl, propyl, isopropyl, butyl,sec-butyl, tert-butyl or isobutyl, preferably methyl or ethyl, and inparticular methyl.

C₁-C₄alkoxy R₁, R₁′, R₂, R₄, R₈ and R₉ independently of one another are,for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy,preferably methoxy or ethoxy, and in particular methoxy. C₁-C₄alkoxy R₂is unsubstituted or substituted in the alkyl moiety by hydroxyl orC₁-C₄alkoxy, for example radicals of the formula —O—CH₂CH₂—OH or—O—CH₂CH₂—OCH₃.

Halogen R₁, R₁′, R₂, R₄, R₈ and R₉ independently of one another are, forexample, fluorine, chlorine or bromine, preferably chlorine or bromine,and in particular chlorine.

C₂-C₄alkanoylamino R₁ and R₂ independently of one another are, forexample, acetylamino or propionylamino, in particular acetylamino.

C₂-C₄-alkanoyl R₃ is, for example, acetyl, propionyl or butyryl,preferably acetyl or propionyl, and in particular acetyl.

C₁-C₄alkylsulfonylamino R₂ is, for example, methylsulfonylamino orethylsulfonylamino, in particular methylsulfonylamino.

The leaving group U is, for example, —Cl, —Br, —F, —OSO₃H, —SSO₃H,—OCO—CH₃, —OPO₃H₂, —OCO—C₆H₅, —OSO₂—C₁-C₄alkyl or —OSO₂—N(C₁-C₄alkyl)₂.Preferably, U is a group of the formula —Cl, —OSO₃H, —SSO₃H, —OCO—CH₃,—OCO—C₆H₅ or —OPO₃H₂, in particular —Cl or —OSO₃H, and particularlypreferably —OSO₃H.

The radicals of the formulae (4a) to (4r) are preferably radicals whichcontain no fibre-reactive group. Radicals which are of particularinterest are those of the formulae (4a), (4d), (4e), (4i), (4k), (4n),(4o), (4p), (4q) and (4r), in particular the radicals of the formulae(4a), (4d), (4e), (4o), (4p), (4q) and (4r). The radicals of theformulae (4e), (4o), (4p) and (4q) are of special interest.

Preferred inks are those in which the dye (A) has the formula (5)

in which

R₁₀, R₁₁, R₁₂ and R₁₃ independently of one another are hydrogen orsubstituted or unsubstituted C₁-C₄alkyl,

B₁ is an aliphatic or aromatic bridge member,

F₁ and F₂ independently of one another are a radical of the formula (I),(II), (III) or (IV), and

X₁ and X₂ independently of one another are halogen, hydroxyl,C₁-C₄alkoxy which is unsubstituted or substituted in the alkyl moiety,phenoxy which is unsubstituted or substituted in the phenyl ring,C₁-C₄alkylthio which is unsubstituted or substituted in the alkylmoiety, phenylthio which is unsubstituted or substituted in the phenylring, amino, N-mono- or N,N-di-C₁-C₆alkylamino which are unsubstitutedor substituted in the alkyl moiety, C₅-C₇-cycloalkylamino which isunsubstituted or substituted in the cycloalkyl ring, phenyl- ornaphthylamino or N-C₁-C₄alkyl-N-phenyl- or N-C₁-C₄alkyl-N-naphthylaminowhich are unsubstituted or substituted in the aryl moiety, benzylaminowhich is unsubstituted or substituted in the phenyl moiety, morpholinoor piperidin-1-yl.

Preferred inks are those in which the dye (B) has the formula (6)

and the dye (C) has the formula (7)

in which

R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ independently of one anotherare hydrogen or substituted or unsubstituted C₁-C₄alkyl,

B₂ and B₃ independently of one another are an aliphatic or aromaticbridge member,

A₁, A₂ and A₃ independently of one another are a mono- or disazo radicalcontaining sulfo groups or a radical of the formula (V), (VI) or (VII),

F₃ is a radical of the formula (I), (II), (III) or (IV) and

X₃, X₄, X₅ and X₆ independently of one another are halogen, hydroxyl,C₁-C₄alkoxy which is unsubstituted or substituted in the alkyl moiety,phenoxy which is unsubstituted or substituted in the phenyl ring,C₁-C₄alkylthio which is unsubstituted or substituted in the alkylmoiety, phenylthio which is unsubstituted or substituted in the phenylring, amino, N-mono- or N,N-di-C₁-C₆alkylamino which are unsubstitutedor substituted in the alkyl moiety, C₅-C₇-cycloalkylamino which isunsubstituted or substituted in the cycloalkyl ring, phenyl- ornaphthylamino or N-C₁-C₄alkyl-N-phenyl- or N-C₁-C₄alkyl-N-naphthylaminowhich are unsubstituted or substituted in the aryl moiety, benzylarhinowhich is unsubstituted or substituted in the phenyl moiety, morpholinoor piperidin-1-yl.

Alkyl radicals R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ andR₂₁ are straight-chain or branched. The alkyl radicals can be furthersubstituted, for example by hydroxyl, sulfo, sulfato, cyano or carboxyl.Examples are the following radicals: methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl or tert-butyl, and the corresponding radicalssubstituted by hydroxyl, sulfo, sulfato, cyano or carboxyl. Preferredsubstituents are hydroxyl, sulfo, sulfato or carboxyl, in particularhydroxyl or sulfato, and preferably hydroxyl.

Aliphatic bridge members B₁, B₂ and B₃ are, for example, aC₂-C₁₂alkylene radical, in particular a C₂-C₆alkylene radical, which canbe interrupted by 1, 2 or 3 members from the group consisting of —NH—,—N(CH₃)— or, in particular, —O— and is unsubstituted or substituted byhydroxyl, sulfo, sulfato, cyano or carboxyl. Preferred substituents ofthe alkylene radicals mentioned for B₁, B₂ and B₃ are hydroxyl, sulfo orsulfato, in particular hydroxyl.

Aliphatic bridge members B₁, B₂ and B₃ are furthermore, for example,C₅-C₉-cycloalkylene radicals, such as, in particular, cyclohexyleneradicals. The cycloalkylene radicals mentioned can be unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo,halogen or carboxyl, in particular by C₁-C₄alkyl. Aliphatic bridgemembers B₁, B₂ and B₃ are furthermore methylene-cyclohexylene,ethylene-cyclohexylene or methylene-cyclohexylene-methylene radicalswhich are unsubstituted or substituted in the cyclohexylene ring byC₁-C₄alkyl, in particular methyl.

The radicals of the formulae —N(R₁₁)—B₁—N(R₁₂)—, —N(R₁₅)—B₂—N(R₁₆)— and—N(R₁₉)—B₃—N(R₂₀)— can also be, for example, a radical of the formula

or

in which alk is, for example, C₁-C₄alkylene, for example ethylene.

Aromatic bridge members B₁, B₂ and B₃ are C₁-C₆alkylenephenylene, suchas methylenephenylene, C₁-C₄alkylenephenylene-C₁-C₄alkylene, for examplemethylenephenylenemethylene, or phenylene which are unsubstituted orsubstituted by C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo,halogen or carboxyl, or a radical of the formula

in which the benzene rings I and II are unsubstituted or substituted byC₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or carboxyland L is the direct bond or a C₂-C₁₀alkylene radical, which can beinterrupted by 1, 2 or 3 oxygen atoms,.or L is a bridge member of theformula —CH═CH—, —N═N—, —NH—, —CO—, —NH—CO—, —NH—SO₂— —NH—CO—NH—, —O—,—S— or —SO₂—. Aromatic bridge members B₁, B₂ and B₃ are preferablyphenylene, which can be substituted as mentioned above. Preferably, thearomatic bridge members B₁, B₂ and B₃ are unsubstituted or substitutedby sulfo. B₁, B₂ and B₃ are preferably a C₂-C₁₂alkylene radical, whichcan be interrupted by 1, 2 or 3 members from the group consisting of—NH—, —N(CH₃)— or —O— and is unsubstituted or substituted by hydroxyl,sulfo, sulfato, cyano or carboxyl; or a C₅-C₉cycloalkylene radical,C₁-C₆alkylenephenylene radical or phenylene radical which areunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, sulfo, halogen or carboxyl; or B₁, B₂ and B₃ are aradical of the formula (8), in which the benzene rings I and II areunsubstituted or substituted by C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, sulfo, halogen or carboxyl and L is the direct bondor a C₂-C₁₀alkylene radical, which can be interrupted by 1, 2 or 3oxygen atoms, or L is a bridge member of the formula —CH═CH—, —N═N—,—NH—, —CO—, —NH—CO—, —NH— SO₂—, —NH—CO—NH—, —O—, —S— or —SO₂— ist; orthe radicals of the formulae —N(R₁₁)—B₁—N(R₁₂)—, —N(R₁₅)—B₂—N(R₁₆)— and—N(R₁₉)—B₁—N(R₂₀)— are a piperazine radical of the formula

B₁, B₂ and B₃ are particularly preferably a C₂-C₁₂alkylene radical,which can be interrupted by 1, 2 or 3 members —O— and is unsubstitutedor substituted by hydroxyl, sulfo, sulfato, cyano or carboxyl, or

a phenylene radical which is unsubstituted or substituted by C₁-C₄alkyl,C₁-C₄alkoxy, C₂-C₄alkanoylamino, sulfo, halogen or carboxyl.

B₁, B₂ and B₃ are especially preferably a C₂-C₁₂alkylene radical, inparticular a C₂-C₆alkylene radical, which can be interrupted by 1, 2 or3 members —O— and is unsubstituted or substituted by hydroxyl orsulfato.

Bridge members B₁, B₂ and B₃ of particular interest are C₂-C₆alkyleneradicals, in particular those of the formula —CH₂—CH(R₂₂)— or—(R₂₂)—CH—CH₂—, in which R₂₂ is C₁-C₄alkyl, in particular methyl.

Halogen X₁, X₂, X₃, X₄, X₅ and X₆ independently of one another are, forexample, fluorine, chlorine or bromine, preferably fluorine or chlorine,and in particular chlorine.

C₁-C₄alkoxy X₁, X₂, X₃, X₄, X₅ and X₆ independently of one another are,for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy,isobutoxy or tert-butoxy, in particular methoxy or ethoxy. The radicalsmentioned are unsubstituted or substituted in the alkyl moiety, forexample by C₁-C₄alkoxy, for example methoxy or ethoxy, hydroxyl, sulfoor carboxyl.

C₁-C₄alkylthio X₁, X₂, X₃, X₄, X₅ and X₆ independently of one anotherare, for example, methylthio, ethylthio, propylthio, isopropylthio orbutylthio. The radicals mentioned are unsubstituted or substituted inthe alkyl moiety, for example by C₁-C₄alkoxy, for example methoxy orethoxy; hydroxyl; sulfo or carboxyl. The radicals substituted in thealkyl moiety by one or two radicals from the group consisting ofhydroxyl, sulfo and carboxyl are preferred.

N-mono- or N,N-di-C₁-C₆alkylamino, preferably N-mono- orN,N-di-C₁-C₄alkylamino, X₁, X₂, X₃, X₄, X₅ and X₆ independently of oneanother are, for example, N-methylamino, N-ethylamino, N-propylamino,N-butylamino, N-hexylamino, N,N-dimethylamino or N,N-di-ethylamino. Theradicals mentioned are unsubstituted or substituted in the alkyl moiety,for example by C₂-C₄alkanoylamino, for example acetylamino orpropionylamino; C₁-C₄alkoxy, for example methoxy or ethoxy; hydroxyl;sulfo; sulfato; carboxyl; carbamoyl; sulfamoyl orβ-sulfatoethylsulfonyl. The radicals mentioned are uninterrupted orinterrupted in the alkyl moiety by oxygen. Examples of radicals whichare substituted in the alkyl moiety and which are interrupted in thealkyl moiety by oxygen are N-β-hydroxyethylamino,N,N-di-β-hydroxyethylamino, N-2-(β-hydroxyethoxy)-ethylamino,N-2-[2-(β-hydroxyethoxy)ethoxy]ethylamino, N-β-sulfatoethylamino,N-β-sulfoethylamino, N-carboxymethylamino, N-β-carboxyethylamino,N-α,β-dicarboxyethylamino, N-α,γ-dicarboxypropylamino,N-ethyl-N-β-hydroxyethylamino and N-methyl-N-β-hydroxyethylamino. Theradicals which are substituted in the alkyl moiety by hydroxyl; sulfo;sulfato; carboxyl or carbamoyl are preferred.

C₅-C₇cycloalkylamino X₁, X₂, X₃, X₄, X₅ and X₆ independently of oneanother can include both the unsubstituted radicals and the radicalswhich are substituted in the cycloalkyl ring, for example by C₁-C₄alkyl,for example methyl or ethyl, in particular methyl, or carboxyl.Preferred such radicals are the corresponding cyclohexyl radicals.

Phenylamino or N-C₁-C₄alkyl-N-phenylamino, preferably phenylamino, X₁,X₂, X₃, X₄, X₅ and X₆ independently of one another can include both theunsubstituted radicals and the radicals which are substituted in thephenyl ring, for example by C₁-C₄alkyl, for example methyl or ethyl,which is unsubstituted or further substituted, for example by carboxyl;C₁-C₄alkoxy, for example methoxy or ethoxy; carboxyl; carbamoyl;N-C₁-C₄alkylcarbamoyl, which is unsubstituted or further substituted inthe alkyl moiety, for example by carboxyl, for exampleN-carboxymethylcarbamoyl; sulfo or halogen, for example chlorine orbromine. The substituted radicals, preferably the radicals substitutedby carboxyl, carboxymethyl, N-carboxymethylcarbamoyl or sulfo, inparticular sulfo, are preferred.

Naphthylamino or N-C₁-C₄alkyl-N-naphthylamino, preferably naphthylamino,X₁, X₂, X₃, X₄, X₅ and X₆ independently of one another can include boththe unsubstituted radicals and the radicals substituted in the naphthylring, for example by sulfo. The radicals substituted by 1 to 3, inparticular 2 to 3, sulfo groups are preferred.

Benzylamino X₁, X₂, X₃, X₄, X₅ and X₆ which are unsubstituted orsubstituted in the phenyl moiety independently of one another caninclude both the unsubstituted radicals and the radicals substituted inthe phenyl ring, for example by C₁-C₄alkyl, for example methyl or ethyl;C₁-C₄alkoxy, for example methoxy or ethoxy; carboxyl; sulfo or halogen,for example chlorine or bromine. The radicals substituted in the phenylring by carboxyl are preferred.

X₁, X₂, X₃, X₄, X₅ and X₆ are preferably halogen, C₁-C₄alkoxy, oralkylthio which are unsubstituted or substituted in the alkyl moiety byC₁-C₄alkoxy, hydroxyl, sulfo or carboxyl, N-mono, orN,N-di-C₁-C₄alkylamino which are unsubstituted or substituted in thealkyl moiety by C₂-C₄alkanoylamino, C₁-C₄alkoxy, hydroxyl, sulfo,sulfato, carboxyl, carbamoyl or sulfamoyl, C₅-C₇-cycloalkylamino whichis unsubstituted or substituted by C₁-C₄alkyl or carboxyl, phenylaminoor N-C₁-C₄alkyl-N-phenylamino which are unsubstituted or substituted inthe phenyl moiety by C₁-C₄alkyl, which is unsubstituted or furthersubstituted by carboxyl, C₁-C₄alkoxy, carboxyl, carbamoyl,N-C₁-C₄alkylcarbamoyl, which is unsubstituted or further substituted inthe alkyl moiety by carboxyl, sulfo or halogen, naphthylamino which issubstituted in the aryl moiety by sulfo, or benzylamino which isunsubstituted or substituted in the phenyl moiety by C₁-C₄alkyl,C₁-C₄alkoxy, carboxyl, sulfo or halogen.

X₁, X₂, X₃, X₄, X₅ and X₆ particularly preferably independently of oneanother are halogen, C₁-C₄alkylthio which is unsubstituted orsubstituted in the alkyl moiety by hydroxyl, sulfo or carboxyl, inparticular sulfo or carboxyl, N-mono- or N,N-di-C₁-C₄alkylamino which isunsubstituted or substituted in the alkyl moiety by C₂-C₄alkanoylamino,C₁-C₄alkoxy, hydroxyl, sulfo, sulfato, carboxyl or carbamoyl, inparticular hydroxyl, sulfo or carboxyl, or morpholino.

R₁₀, R₁₃, R₁₄, R₁₇, R₁₈ and R₂₁ are preferably hydrogen or C₁-C₄alkyl,in particular hydrogen.

R₁₁, R₁₂, R₁₅, R₁₆, R₁₉ and R₂₀ are preferably hydrogen or C₁-C₄alkylwhich is unsubstituted or substituted by hydroxyl, sulfo, sulfato orcarboxyl, preferably hydrogen or C₁-C₄alkyl, and in particular hydrogen.

The radicals F₁ and F₂ in the dye of the formula (5) can be different oridentical. Preferably, the radicals F₁ and F₂ are identical.

The radicals A₁ and A₂ in the dye of the formula (6) can be different oridentical. Preferably, the radicals A₁ and A₂ are identical.

The radicals X₁ and X₂ in the dye of the formula (5) can be different oridentical. Preferably, the radicals X₁ and X₂ are identical.

The radicals X₃ and X₄ in the dye of the formula (6) can be different oridentical. Preferably, the radicals X₃ and X₄ are identical.

The radicals X₅ and X₆ in the dye of the formula (7) can be different oridentical. Preferably, the radicals X₅ and X₆ are identical.

Preferred inks are those in which the dye (A) has the formula (5), thedye (B) has the formula (6) and the dye (C) has the formula (7), inwhich R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, B₁,B₂, B₃, F₁, F₂, F₃, A₁, A₂, A₃, X₁, X₂, X₃, X₄, X₅ and X₆ are as definedand preferred above under formulae (5), (6) and (7).

Particularly preferred inks are those in which the dye (A) has theformula (5), the dye (B) has the formula (6) and the dye (C) has theformula (7), in which

R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ arehydrogen, B₁, B₂ and B₃ independently of one another are a radical ofthe formula —CH₂—CH(R₂₂)— or —(R₂₂)—CH—CH₂—, in which R₂₂ is C₁-C₄alkyl,in particular methyl,

F₁, F₂ and F₃ independently of one another are a radical of the formula(I), (II), (III), (IVa), (IVb) or (IVc), in particular (I.1), (I.2),(I.3), (I.4), (I.5), (II.1), (II.2), (II.3), (III.1), (IVb) or (IVc),A₁, A₂ and A₃ independently of one another are a radical of the formula(4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j), (4k), (41),(4m), (4n), (40), (4p), preferably (4a), (4d), (4e), (4o), (4p), (4q),(4r), (V), (VI) or (VII), and in particular (4e), (4o), (4p), (4q), (V),(VI) or (VII), which contain no fibre-reactive substituents, and

X₁, X₂, X₃, X₄, X₅ and X₆ independently of one another are halogen,C₁-C₄alkylthio which is unsubstituted or substituted in the alkyl moietyby hydroxyl, sulfo or carboxyl, in particular sulfo or carboxyl, N-mono-or N,N-di-C₁-C₄alkylamino which are unsubstituted or substituted in thealkyl moiety by C₂-C₄alkanoylamino, C₁-C₄alkoxy, hydroxyl, sulfo,sulfato, carboxyl or carbamoyl, in particular hydroxyl, sulfo orcarboxyl, or morpholino.

A particularly preferred embodiment of the present invention comprisesinks which comprise at least one dye (A) of the formula (5) togetherwith at least one dye (C) of the formula (7), in which

R₁₀, R₁₁, R₁₂, R₁₃, R₁₈, R₁₉, R₂₀, R₂₁, B₁, B₃, F₁, F₂, F₃, A₃, X₁, X₂,X₅ and X₆ are as defined and preferred above.

Further suitable dyes (C) for the inks according to the invention havethe formula (9)

in which

R₂₃ is as defined and preferred for R₁₀, R₁₃, R₁₄, R₁₇, R₁₈ and R₂₁,

R₂₄ and R₂₅ independently of one another are as defined and preferredfor R₁₁, R₁₂, R₁₅, R₁₆,

R₁₉ and R₂₀,

B₄ is as defined and preferred for B₁, B₂ and B₃,

A₄ is a radical of the formula (VII),

F₄ is as defined and preferred for F₁, F₂ and F₃ and

X₇ is as defined and preferred for X₁, X₂, X₃, X₄, X₅ and X₆.

The inks according to the invention preferably comprise 30 to 95% byweight of at least one dye (A) together with 5 to 70% by weight of atleast one dye chosen from the group consisting of (B) and (C), based onthe total weight of dyes (A), (B) and (C) in the ink.

If the ink according to the invention comprises at least one dye (A)together with at least one dye (B), the dye (A) is present, for example,in an amount of 60 to 95% by weight, preferably 70 to 95% by weight, inparticular 75 to 90% by weight, and the dye (B) is present, for example,in an amount of 5 to 40% by weight, preferably 5 to 30% by weight, andin particular 10 to 25% by weight, based on the total weight of the dyes(A) and (B) in the ink.

If the ink according to the invention comprises at least one dye (A)together with at least one dye (C), the dye (A) is present, for example,in an amount of 25 to 90% by weight, preferably 30 to 80% by weight, andin particular 30 to 70% by weight, and the dye (C) is present, forexample, in an amount of 10 to 75% by weight, preferably 20 to 70% byweight, and in particular 30 to 70% by weight, based on the total weightof the dyes (A) and (C) in the ink.

The inks according to the invention can comprise further dyes forshading, in addition to the abovementioned dyes. Preferably, the inkscomprise no substantial amounts of a further dye which does not fallunder the definition according to the claims of the dyes in the inksaccording to the invention. “Substantial amounts” in this connection isto be understood as meaning, for example, amounts of more than 5% byweight, based on the total weight of the dyes (A), (B) and (C) in theink.

The dyes used in the inks according to the invention should preferablyhave a low salt content, i.e. comprise a total content of salts of lessthan 0.5% by weight, based on the weight of the dyes. Dyes which haverelatively high salt content due to their preparation and/or thesubsequent addition of diluents can be desalinated, for example, bymembrane separation processes, such as ultrafiltration, reverse osmosisor dialysis.

The inks preferably comprise a total content of dyes of 1 to 35% byweight, in particular 1 to 30% by weight, and preferably 1 to 20% byweight, based on the total weight of ink. A limit of 2.5% by weight, inparticular 5% by weight, and preferably 7.5% by weight, is preferredhere as the lower limit.

Those inks which have a viscosity of 1 to 40 mPas (millipascal-seconds)are preferred.

The inks comprise water-miscible solvents in an amount of 1 to 40% byweight, for example C₁-C₄ alcohols, for example methanol, ethanol,n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol orisobutanol; amides, for example dimethylformamide or dimethylacetamide,ketones or ketone alcohols, for example acetone or diacetone alcohol;ethers for example tetrahydrofuran or dioxane; nitrogen-containingheterocyclic compounds, for example N-methyl-2-pyrrolidone or1,3-dimethyl-2-imidazolidone, polyalkylene glycols, for examplepolyethylene glycol or polypropylene glycol; C₂-C₆alkylene glycols andthioglycols, for example ethylene glycol, propylene glycol, butyleneglycol, triethylene glycol, thiodiglycol, hexylene glycol and diethyleneglycol; further polyols, for example glycerol or 1,2,6-hexanetriol; andC₁-C₄alkyl ethers of polyhydric alcohols, for example 2-methoxyethanol,2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy)ethanol,2-[2-(2-methoxyethoxy)ethoxy]ethanol or2-[2-(2-ethoxyethoxy)ethoxy]ethanol; preferably N-methyl-2-pyrrolidone,diethylene glycol, glycerol or, in particular, 1,2-propylene glycol,preferably in an amount of 2 to 30% by weight, in particular 5 to 30% byweight, and especially 10 to 25% by weight, based on the total weight ofthe ink.

The inks can furthermore also comprise solubilizing agents,for exampleε-caprolactam.

The inks can comprise thickeners of natural or synthetic origin, interalia for the purpose of adjusting the viscosity.

Examples of thickeners are commercially available alginate thickeners,starch ethers or carob bean flower ethers, in particular sodiumalginate, by itself or as a mixture with modified cellulose, for examplemethyl-, ethyl-, carboxymethyl-, hydroxyethyl-, methylhydroxyethyl-,hydroxypropyl- or hydroxypropylmethylcellulose, in particular withpreferably 20 to 25% by weight of carboxymethylcellulose. Syntheticthickeners are furthermore, for example, those based onpoly(meth)acrylic acids or poly(meth)acrylamides.

The inks comprise such thickeners, for example, in an amount of 0.01 to2% by weight, in particular 0.01 to 1% by weight, and preferably 0.01 to0.5% by weight, based on the total weight of the ink.

The inks can furthermore comprise buffer substances, for example borax,borate, phosphate, polyphosphate or citrate. Examples are borax, sodiumborate, sodium tetraborate, sodium dihydrogenphosphate, disodiumhydrogen phosphate, sodium tripolyphosphate, sodium tripolyphosphate,sodium pentaphosphate and sodium citrate. They are used, in particular,in amounts of 0.1 to 3% by weight, preferably 0.1 to 1% by weight, basedon the total weight of the ink, in order to establish a pH of, forexample, 4 to 10, preferably 5 to 8.

The inks can comprise surfactants or humectants as further additives.

Surfactants are the commercially available anionic or nonionicsurfactants. Humectants are, for example, urea, glycerol, propyleneglycol or a mixture of sodium lactate (advantageously in the form of a50 to 60% aqueous solution) and glycerol and/or propylene glycol inamounts of preferably 0.1 to 30% by weight, in particular 2 to 30% byweight, in the inks according to the invention.

If desired, the inks can also comprise acid donors, such asbutyrolactone or sodium hydrogen phosphate, preservatives, substanceswhich inhibit fungal and/or bacterial growth, foam suppressants,sequestering agents, emulsifiers, water-insoluble solvents, oxidizingagents or de-aerating agents.

Preservatives are, in particular, formaldehyde-releasing agents, forexample paraformaldehyde and trioxane, in particular aqueous,approximately 30 to 40% by weight formaldehyde solutions, sequesteringagents are, for example, sodium nitrilotriacetate, sodiumethylenediaminetetraacetate, and in particular sodium polymetaphosphate,especially sodium hexametaphosphate, emulsifiers are, in particular,adducts of an alkylene oxide and a fatty alcohol, in particular anadduct of oleyl alcohol and ethylene oxide, water-insoluble solvents arehigh-boiling saturated hydrocarbons, in particular paraffins with aboiling range from about 160 to 210° C. (so-called white spirits)oxidizing agents are, for example, an aromatic nitro compound, inparticular an aromatic mono- or dinitrocarboxylic acid or -sulfonicacid, which may be present as an alkylene oxide adduct, in particular anitrobenzenesulfonic acid, and de-aerating agents are, for example,high-boiling solvents, in particular terpentine oils, higher alcohols,preferably C₈ to C₁₀ alcohols, terpene alcohols or de-aerating agentsbased on mineral and/or silicone oils, in particular commercialformulations of about 15 to 25% by weight of a mixture of mineral oiland silicone oil and about 75 to 85% by weight of a C₈ alcohol, forexample 2-ethyl-n-hexanol. These are usually used in amounts of 0.01 to5% by weight based on the total weight of the ink.

The inks can be prepared in the customary manner by mixing theindividual constituents into the desired amount of water. If necessary,the inks are clarified by filtration through an extra-fine filter.

The inks according to the invention are suitable, for example, forprinting. Examples of appropriate printing processes are conventionalprinting, screen printing and inkjet printing processes.

The inks according to the invention are particularly suitable for use inrecording systems of a type in which an ink is pressed out of a smallopening in the form of droplets directed against a substrate on which animage is formed. Suitable substrates are, for example, textile fibrematerials, paper or films of plastic. Suitable recording systems are,for example, commercially available ink-jet printers for use in printingof paper or textiles, or writing implements, such as fountain pens orball-point pens, and in particular ink-jet printers.

It may be necessary, for example, to adjust the viscosity or otherphysical properties of the ink, in particular those which have aninfluence on the affinity for the particular substrate, according to themethod of use.

The inks according to the invention which comprise dyes withfibre-reactive radicals are thus suitable for use in the printing ofpaper or textiles.

Inks which comprise dyes without fibre-reactive radicals areparticularly suitable for recording on paper, and especially for use inthe printing of paper.

Textile fibre materials are, in particular, fibre materials containingnitrogen or containing hydroxyl groups, for example textile fibrematerials of cellulose, silk, wool or synthetic polyamides.

Examples of paper which can be printed with the inks according to theinvention are commercially available ink-jet paper, photographic paper,glazed paper and paper coated with plastic, for example Epson Ink-JetPaper, Epson Photo Paper, Epson Glossy Film, HP Special Ink Jet Paper,Encad Photo Gloss Paper and IIford Photo Paper. Films of plastic whichcan be printed with the inks according to the invention are, forexample, transparent or milky/opaque. Suitable films of plastic are, forexample, 3M Transparency-Film.

The present invention thus also relates to a process for printing paper,films of plastic or textile fibre materials, in particular by theink-jet printing process, which comprises using an aqueous ink whichcomprises

20 to 95% by weight of at least one dye (A) together with 5 to 80% byweight of at least one dye chosen from the group consisting of (B) and(C), based on the total weight of the dyes (A),(B) and (C) in the ink,and

1 to 40% by weight of a water-miscible organic solvent , based on thetotal weight of the ink, wherein

the dyes (A), (B) and (C) are as defined and preferred above.

In the case of the ink-jet printing process, individual drops of the inkare sprayed out of a jet in a controlled manner onto a substrate. Thecontinuous ink-jet method and the drop-on-demand method are chiefly usedfor this. In the case of the continuous ink-jet method, the drops areproduced continuously, drops which are not required for printing beingdiverted into a collecting container and recycled. In the case of thedrop-on-demand method, on the other hand, drops are produced and printedas required, i.e. drops are only produced if this is necessary forprinting. The drops can be produced, for example, by means of a piezoink-jet head or by means of thermal energy (bubble jet). Printing bymeans of a piezo ink-jet head is preferred for the process according tothe invention. Printing by the continuous ink-jet method is furthermorepreferred for the process according to the invention.

The records produced, such as, for example, prints, are distinguished bygood black shades without a change in shade in artificial light(metamerism) with an outstanding fastness to light. Records which areproduced with inks comprising a dye (A) together with a dye (C) show no“orange bleeding” of the black shade.

The present invention also relates to black-dyeing dye mixtures whichcomprise 20 to 95% by weight of at least one dye (A) together with 5 to80% by weight of at least one dye chosen from the group consisting of(B) and (C), based on the total weight of the dyes (A), (B) and (C) inthe dye mixture, where the dye (A) has the formula (5), the dye (B) hasthe formula (6) and the dye (C) has the formula (7), in which theradicals R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, B₁,B₂, B₃, F₁, F₂, F₃, A₁, A₂, A₃, X₁, X₂, X₃, X₄, X₅ and X₆ are as definedand preferred above under the formulae (5), (6) and (7).

The dye mixtures according to the invention can be prepared, forexample, by mixing the individual dyes. This mixing process is carriedout, for example, in suitable mills, for example ball or pinned discmills, and in kneaders or mixers.

The dye mixtures according to the invention in which the dye (A) has theformula (5), the dye (B) has the formula (6) and the dye (C) has theformula (7) and the radicals R₁₀, R₁₃ and R₂₁; R₁₁, R₁₂, R₁₅, R₁₆, R₁₉and R₂₀; R₁₄, R₁₇ and R₁₈; B₁, B₂ and B₃; F₁, F₂ and F₃; A₁, A₂ and A₃and X₁, X₂, X₃, X₄, X₅ and X₆ in each case have identical meanings, canbe prepared by reacting the compounds of the formulae (10a) and (10b)

F₁—N(R₁₀)H  (10a)

and

A₁—N(R₁₄)H  (10b)

or corresponding dye intermediates, a halogenotriazine compound of theformula (11)

and a diamine of the formula (12)

in which A₁, F₁, R₁₀, R₁₁, R₁₂ and R₁₄ are as defined under the formulae(5) and (6), and X is halogen, for example fluorine or chlorine, withone another in any sequence and, in the case where dye intermediates areused, the resulting intermediate products are converted into the desireddyes, and, if appropriate, a further reaction with a compound of theformula (13)

H—X₁  (13)

in which X₁ is as defined under the formula (5), with the exception ofhalogen, follows.

The preparation of the end dyes from the intermediates is, inparticular, coupling reactions which lead to azo dyes.

Since the individual process steps described above can be carried out ina different sequence, and in some cases also at the same time, ifappropriate, various process variants are possible. In general, thereaction is carried out stepwise in succession, the sequence of thesimple reactions between the individual reaction componentsadvantageously depending on the particular conditions.

One process variant comprises reacting the compounds of the formulae(10a) and (10b) independently of one another with in each case anapproximately equivalent amount of a halogenotriazine compound of theformula (11) to give the compounds of the formulae (14a) and (14b)

and then subjecting a mixture of approximately two molar equivalents ofthe compounds of the formulae (14a) and (14b) to a condensation reactionwith approximately one molar equivalent of a diamine of the formula (12)and, if appropriate, following this condensation step with a furtherreaction with a compound of the formula (13).

The ratio of the dyes of the formulae (5), (6) and (7) in the mixturecan vary in the range stated and depends here on the ratio of thecompounds of the formulae (14a) and (14b) in the reaction mixture.

The individual condensation reactions are carried out, for example, byprocesses which are known per se, as a rule in aqueous solution at atemperature of, for example, 0 to 50° C. and a pH of, for example, 4 to10.

The present invention relates to a process for the preparation of thedye mixtures according to the invention which do not comprisesubstantial amounts of a compound of the formula (6), which comprises

(i) reacting the compounds of the formulae (10a) and (10b) independentlyof one another with in each case a halogenotriazine compound of theformula (11) to give the compounds of the formulae (14a) and (14b),

(ii) reacting the compound of the formula (14b) with an excess of adiamine of the formula (12) such that a mixture of the compounds of theformulae (12) and (15)

 is obtained,

(iii) subjecting this mixture to a condensation reaction with a compoundof the formula (14a) in an equimolar amount which corresponds to thenumber of amino groups which have not been acylated by the compound ofthe formula (14b), to give a mixture of the compounds of the formulae(5a) and (7a)

 and

(iv) if appropriate reacting the radicals X with a compound of theformula (13), in which A₁, F₁, R₁₀, R₁₁, R₁₂ and R₁₄ are as defined andpreferred under the formulae (5) and (6), X is halogen, for examplefluorine or chlorine, and X₁ is as defined and preferred under theformula (5), and is not halogen.

The ratio of the dyes of the formulae (5a) and (7a) in the mixture canvary in the range stated and depends here on the ratio of the compoundsof the formulae (12) and (14b) according to process step (ii), the molarratio of the compounds of the formulae (12) and (14b) being greater than1 and, for example, 1.5 to 10, and preferably 2 to 6. Process step (ii)is advantageously carried out at a pH of 5 to 7.

The compounds of the formulae (10a), (10b), (12) and (13) are known orcan be obtained analogously to known compounds.

The present invention furthermore relates to dyes of the formula (9)

in which

R₂₃ is as defined and preferred for R₁₀, R₁₃, R₁₄, R₁₇, R₁₈ and R₂₁,

R₂₄ and R₂₅ independently of one another are as defined and preferredfor R₁₁, R₁₂, R₁₅, R₁₆,

R₁₉ and R₂₀,

B₄ is as defined and preferred for B₁, B₂ and B₃,

A₄ is a radical of the formula (VIII),

F₄ is as defined and preferred for F₁, F₂ and F₃ and

X₇ is as defined and preferred for X₁, X₂, X₃, X₄, X₅ and X₆.

Dyes of the formula (9) can be prepared by an addition reaction of acompound of the formula (16)

with a compound of the formula (17)

in which the radicals R₂₃, R₂₄, R₂₅, B₄, F₄ and W are as defined andpreferred above and X is halogen, for example fluorine or chlorine, inthe presence of a base, for example an alkali metal hydroxide, inparticular sodium hydroxide, at a pH of, for example, 7 to 12,preferably 8 to 10.

If appropriate, the radical X₇ can be introduced by first reacting thecompound of the formula (16) or the resulting addition product of thecompounds of the formulae (16) and (17) with a compound of the formulaH—X₇, in which X₇ is as defined and preferred, with the exception ofhalogen, by processes known per se.

The compounds of the formula (16) and (17) are known or can be preparedby processes known per se.

The present invention also relates to dyes (C) of the formula (18)

in which

R₂₆, R₂₇, R₂₈ and R₂₉ independently of one another are hydrogen orsubstituted or unsubstituted C₁-C₄alkyl,

B₅ is an aromatic bridge member and

F₅ is a radical of the formula (I), (II), (III), (IVa), (IVb) or (IVc),in particular (I.1), (I.2), (I.3) (I.4), (I.5), (II.1), (II.2), (II.3),(III.1), (IVb) or (IVc),

A₄ is a radical of the formula (4a), (4b), (4c), (4d), (4e), (4f), (4g),(4h), (4i), (4j), (4k), (4l), (4m), (4n), (4o), (4p), (4q), (4r), (V),(VI) or (VII), preferably (4a), (4d), (4e), (4o), (4p), (4q), (4r), (V),(VI) or (VII), and in particular (4e), (4o), (4p), (4q), (V), (VI) or(VII), and

X₈ and X₉ are as defined and preferred above for X₁, X₂, X₃, X₄, X₅ andX₆.

R₂₆ and R₂₉ are as defined and preferred above for R₁₀, R₁₃, R₁₄, R₁₇,R₁₈ and R₂₁.

R₂₇ and R₂₈ are as defined and preferred above for R₁₁, R₁₂, R₁₅, R₁₆,R₁₉ and R₂₀.

A4 is as defined and preferred above for radicals A₁, A₂ and A₃ of theformulae (4a), (4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j),(4k), (41), (4m), (4n), (4o), (4p), (4q), (4r), (V), (VI) and (VII).

B₅ is as defined and preferred above for aromatic bridge members B₁, B₂and B₃.

F₅ is as defined and preferred above for radicals F₁, F₂ and F₃ of theformulae (I), (II), (III), (IVa), (IVb) and (IVc).

The present invention also relates to dyes (C) of the formula (18) inwhich

R₂₆, R₂₇, R₂₈ and R₂₉ are as defined and preferred above,

B₅ is an aliphatic bridge member,

F₅ is as defined and preferred above,

A₄ is a radical of the formula (4o)

 in which

(R₁)₀₋₃ is 0 to 3 identical or different substituents from the groupconsisting of C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, halogen,carboxyl and sulfo, in particular a sulfo group,

(R₁′)₀₋₃ is 0 to 3 identical or different substituents from the groupconsisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl and sulfo, inparticular a sulfo group,

(R₂)₀₋₃ is 0 to 3 identical or different substituents from the groupconsisting of halogen, nitro, cyano, trifluoromethyl, sulfamoyl,carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxy which is unsubstituted or substitutedby hydroxyl or C₁-C₄alkoxy, amino, C₂-C₄alkanoylamino, ureido, hydroxyl,carboxyl, sulfomethyl, C₁-C₄alkylsulfonylamino and sulfo, in particularhalogen, C₁-C₄alkyl, C₁-C₄alkoxy which is unsubstituted or substitutedby hydroxyl or C₁-C₄alkoxy, amino, C₂-C₄alkanoylamino, ureido,C₁-C₄alkylsulfonylamino and sulfo, and

Z is vinyl or a radical —CH₂-CH₂—U and U is a leaving group, and

X₈ and X₉ are as defined and preferred above.

The radical A₄ preferably contains no fibre-reactive group of theformula —SO₂—Z.

B₅ is as defined and preferred above for aliphatic bridge members B₁, B₂and B₃.

The dyes of the formula (18) according to the invention can be preparedby processes known per se, such as are described, for example, in U.S.Pat. No. 5,684,138.

The invention also relates to a process for dyeing or printing fibrematerials containing hydroxyl groups or containing nitrogen with thedyes or dye mixtures according to the invention.

Fibre materials are, for example, the natural cellulosic fibres, such ascotton, linen, jute or hemp, and modified cellulosic fibres, such ascellulose or regenerated cellulose. The dyes and dye mixtures accordingto the invention are also suitable for dyeing or printing naturalpolyamide fibre materials, for example silk or wool, synthetic polyamidefibre materials, for example polyamide 6 or polyamide 6.6, or wool andsynthetic polyamide blend fabrics. The dyes and dye mixtures accordingto the invention are particularly suitable for dyeing or printingnatural polyamide fibre materials, and here in particular wool orchlorinated wool or wool with a washing machine-resistant finish.

The textile fibre materials mentioned can be in the most diverse formsof processing here, for example as fibre, yarn, fluff, woven fabric orknitted fabric.

The dyes and dye mixtures according to the invention are suitable forcustomary dyeing and printing processes and can be applied and fixed tothe fibre material in the most diverse ways, in particular in the formof aqueous dye solutions or printing pastes. They are suitable both forthe exhaust method and for pad dyeing, in which the goods areimpregnated with aqueous dye solutions, which may contain salts, and thedyes are fixed after an alkali treatment or in the presence of alkali,with the action of heat if appropriate. The dyes and dye mixturesaccording to the invention are also suitable for the so-called coldpad-batch process, in which the dye is applied on the padder togetherwith the alkali and is then fixed by storage at room temperature forseveral hours.

Dyeing of natural and synthetic polyamide fibre materials, in particularwool, is preferably carried out by the exhaust method at a pH of about 3to 7, in particular 4 to 6, and at temperatures of, for example, 70 to120° C., and in particular 90 to 105° C.

In addition to water and the dyes or dye mixtures according to theinvention, the dye liquors or printing pastes can comprise furtheradditives, for example shading dyes, salts, buffer substances, wettingagents, antifoams, levelling agents or agents which influence theproperties of the textile material, for example softening agents,additives for a flame-retardant finish or soil-, water- andoil-repellent agents, as well as water-softening agents and natural orsynthetic thickeners, for example alginates or cellulose ethers, theseadditives being known per se.

The dyes and dye mixtures according to the invention give level dyeingsand prints with good allround properties, in particular good fastness towashing, rubbing, wet processing, wet rubbing and light. The dyes anddye mixtures according to the invention are furthermore distinguished bya uniform colour build-up, good affinity and high degrees of fixing.Furthermore, the otherwise customary after-treatment of the dyeings andprints with so-called fixing agents can be omitted in the case of thedyes and dye mixtures according to the invention.

The dye mixtures according to the invention in which the dye (A) has theformula (5), the dye (B) has the formula (6) and the dye (C) has theformula (7) and the dyes according to the invention has the formula (9)and (18) are furthermore distinguished by a good solubility.

In the following examples parts are parts by weight. The temperaturesare degrees Celsius. Parts by weight and parts by volume bear the samerelationship as the gram and cubic centimetre.

EXAMPLE 1

a) 9.22 parts of cyanuric chloride are suspended in 150 parts ofice-water. The pH is brought to 5 with 1 N sodium hydroxide solution andthe temperature is kept at 0 to 2° C. A neutral solution of 29.80 partsof the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid in 250 parts of water is added to this suspension at 0 to 3° C.During the addition the pH is kept at 5 with a 2 N sodium hydroxidesolution. After the addition, the mixture is stirred at 0 to 3° C. andpH 5 for about a further 2 hours. A solution of5-[4,6-dichloro-1,3,5-triazin-2-ylamino]-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid is obtained.

b) 3.56 parts of cyanuric chloride are suspended in 50 parts ofice-water. The pH is brought to 5.5 with 1 N sodium hydroxide solutionand the temperature is kept at 0 to 2° C. A neutral solution of 10.02parts of 4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acidin 120 parts of water is added to this suspension at 0 to 3° C. Duringthe addition the pH is kept at 5.5 with 1 N sodium hydroxide solution.After the addition the mixture is stirred at 0 to 5° C. and pH 5.5 forabout a further 3 hours. A suspension of4-[2-ureido-4-(4,6-dichloro-1,3,5-triazin-2-ylamino)phenylazo]-azobenzene-3,4′-disulfonicacid is obtained.

c) The suspension obtained according to b) is added dropwise to asolution of 2.31 parts of 1,2-diaminopropane in 50 parts of ice-water,which has been brought to pH 5.5 to 6 with 16% hydrochloric acid, the pHbeing kept at 6 with 1 N sodium hydroxide solution. During the dropwiseaddition the temperature is allowed to rise to about 20° C. To bring thereaction to completion the temperature is increased to 50° C. in thecourse of several hours and the pH is increased to 6.5 to 7.

d) The solution obtained according to a) is allowed to run slowly intothe solution obtained according to c), the pH being kept at 6.5 byaddition of a 1N sodium hydroxide solution and the temperature beingkept at 15 to 20° C. To bring the reaction to completion the temperatureis increased to 50° C. and the pH is increased to 8.5 to 9. A few dropsof 1,2-diaminopropane are added to the reaction mixture at a temperatureof 35 to 40° C. in order to eliminate an excess of the compoundaccording to process step a) in the reaction mixture. The pH isincreased to 10 by addition of a 2 N sodium hydroxide solution. Thereaction mixture is then allowed to cool to room temperature and the pHis brought to 8 with 2 N hydrochloric acid. The reaction mixture isclarified by filtration, and freed from the salt by dialysis and theresulting solution is freeze-dried. 54.6 parts of a dye mixture whichcomprises about 46% by weight of a dye which, in the form of the freeacid, has the formula (101)

and 54% by weight of a dye which, in the form of the free acid, has theformula (102)

in which

F₁ is a radical of the formula (103)

A₁ is a radical of the formula (104)

and B₁ is a radical of the formula

 are obtained.

The dye mixture gives prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLE 2

a) 9.65 parts of cyanuric fluoride are added to a neutral solution of35.80 parts of the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid in 350 parts of water at 0 to 2° C. in the course of 10 minutes.During the addition the pH is kept at 5.8 to 6 with a 15% sodiumhydroxide solution. After the addition the mixture is stirred for about15 minutes, the pH is brought to 3.5 to 3.8 with 32% hydrochloric acidand the mixture is stirred again for about 15 minutes. The pH is thenbrought to about 5.8 to 6 with a 15% sodium hydroxide solution. Asolution of5-[4,6-difluoro-1,3,5-triazin-2-ylamino]-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid is obtained.

b) 3.38 parts of cyanuric fluoride are slowly added to a neutralsolution of 10.02 parts of4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acid in 120parts of water at 0 to 2° C. During the addition the pH is kept at 7.3to 7.5 with a 15% sodium hydroxide solution. After the addition themixture is stirred at 0 to 2° C. for about 10 minutes and the pH is keptat 7.3 to 7.5. The pH is then brought to 3.5 with 32% hydrochloric acidand the mixture is stirred again at 0° C. for about 10 minutes. Asolution of4-[2-ureido-4-(4,6-difluoro-1,3,5-triazin-2-ylamino)phenylazo]-azobenzene-3,4′-disulfonicacid is obtained.

c) The cold solution (0° C.) obtained according to b) is slowly addeddropwise to a solution of 2.31 parts of 1,2-diaminopropane in 50 partsof water at 2° C. and a pH of 6 to 6.5. The pH is kept at 6 to 6.5 herewith 1 N sodium hydroxide solution and the temperature is kept at 20 to25 C. To bring the reaction to completion the mixture is stirred underthese conditions for a few hours.

d) The suspension obtained according to c) is cooled to 0 to 5° C. andthe pH is brought to 8.5 with a 15% sodium hydroxide solution. Thesolution obtained according to a) is then metered in, the pH being keptat 8.5 with 15% sodium hydroxide solution. The temperature is slowlyincreased to 20 to 25° C. and the pH to 9. To bring the reaction tocompletion the mixture is stirred under these conditions for some hours.The resulting solution is then rendered neutral, clarified byfiltration, freed from the salt by dialysis and freeze-dried. 42.8 partsof a dye mixture which comprises about 46% by weight of a dye which, inthe form of the free acid, has the formula (105)

and 54% by weight of a dye which, in the form of the free acid, has theformula (106)

in which

F₁ is a radical of the formula (103), A₁ is a radical of the formula(104) and

B₁ is a radical of the formula

 are obtained.

The dye mixture gives prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLE 3

10.7 parts of the dye mixture obtained according to Example 2d),comprising the dyes of the formulae (105) and (106), are dissolved in200 parts of water, and 1.92 parts of morpholine are added at 20° C. anda pH of 8. The reaction mixture is heated to 50 to 55° C. and the pH isbrought to 10 by addition of 15% sodium hydroxide solution. The mixtureis stirred at this temperature for about a further 1 hour. The reactionmixture is then allowed to cool to room temperature and the pH isbrought to 7 to 7.5 with 16% hydrochloric acid. The resulting solutionis freed from the salt by dialysis and freeze-dried. 11.1 parts of a dyemixture which comprises about 46% by weight of a dye which, in the formof the free acid, has the formula (107)

and 54% by weight of a dye which, in the form of the free acid, has theformula (108)

in which

F₁ is a radical of the formula (103), A₁ is a radical of the formula(104) and

B₁ is a radical of the formula

 are obtained.

The dye mixture gives prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLES 4 TO 30

The procedure described in Example 1 is repeated, using an equimolaramount of a disazo dye A₁—NH₂, in which

A₁ is a radical of the formula

and R₁, R₁′, R₂ and R₂′ are each as defined in Table 1,

in place of 10.02 parts of4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acid. A mixtureof dyes which, in the form of the free acid, have the formulae (101) and(102), in which

F₁ is a radical of the formula (103),

A₁ has the formula (104a), in which R₁, R₁′, R₂ and R₂′ are each asdefined in Table 1,

and B₁ is a radical of the formula

 is obtained.

TABLE 1 Example R₁ R₁′ R₂ R₂′  4 (31) 4-SO₃H H —NH—CO—NH₂ —OCH₃  5 (32)4-SO₃H H —NH—CO—NH₂ —OCH₂CH₂—OH  6 (33) 4-SO₃H H —NH—CO—NH₂ —Cl  7 (34)4-SO₃H H —NH—CO—CH₃ H  8 (35) 4-SO₃H H —NH—CO—CH₃ —OCH₃  9 (36) 4-SO₃H H—NH—CO—CH₃ —OCH₂CH₂—OH 10 (37) 4-SO₃H H —NH—CO—CH₃ —Cl 11 (38) 4-SO₃H H—CH₃ H 12 (39) 4-SO₃H H —CH₃ —OCH₃ 13 (40) 4-SO₃H H —CH₃ —OCH₂CH₂—OH 14(41) 4-SO₃H H —CH₃ —Cl 15 (42) 4-SO₃H H —OCH₃ —OCH₃ 16 (43) 4-SO₃H H—OCH₂CH₂—OH —OCH₂CH₂—OH 17 (44) 4-SO₃H H —OCH₂CH₂—OCH₃ —OCH₂CH₂—OCH₃ 18(45) 4-SO₃H H H H 19 (46) 4-SO₃H H —NH—CO—CH₂CH₃ H 20 (47) 4-SO₃H H—NH—CO—CH₂CH₃ —OCH₃ 21 (48) 4-SO₃H H —NH—CO—CH₂CH₃ —OCH₂CH₂—OH 22 (49)4-SO₃H H —NH—CO—CH₂CH₃ —Cl 23 (50) 4-SO₃H H —NH—SO₂—CH₃ H 24 (51) 4-SO₃HH —NH₂ —SO₃H 25 (52) 4-SO₃H H —NH—CO—CH₃ —SO₃H 26 (53) 4-COOH H—NH—CO—NH₂ H 27 (54) 3-COOH 5-COOH —NH—CO—NH₂ H 28 (55) 3-COOH H—NH—CO—NH₂ H 29 (56) 2-COOH 5-COOH —NH—CO—NH₂ H 30 (57) 2-COOH H—NH—CO—NH₂ H

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLES 31 TO 57

The procedure described in Example 2 is repeated, using an equimolaramount of a disazo dye A₁—NH₂, in which

A₁ is a radical of the formula (104a)

and R₁, R₁′, R₂ and R₂′ are each as defined in Table 1,

in place of 10.02 parts of4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acid. A mixtureof dyes which, in the form of the free acid, have the formulae (105) and(106), in which

F₁ is a radical of the formula (103),

A₁ has the formula (104a), in which R₁, R₁′, R₂ and R₂′ are each asdefined in Table 1,

and B₁ is a radical of the formula

 is obtained.

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLES 58 TO 63

The procedure described in Example 1 is repeated, using an equimolaramount of a formazan dye F₁—NH₂, in which F₁ is in each case as definedin Table 2, in place of 29.80 parts of the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid. A mixture of dyes which, in the form of the free acid, have theformulae (101) and (102), in which

F₁ is in each case as defined in Table 2,

A₁ is a radical of the formula (104)

and B₁ is a radical of the formula

 is obtained.

TABLE 2 Example F₁ 58 (64)

59 (65)

60 (66)

61 (67)

62 (68)

63 (69)

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLES 64 TO 69

The procedure described in Example 2 is repeated, except that theequimolar amount of a formazan dye F₁—NH₂, in which F₁ is in each caseas defined in Table 2, is used in place of 35.80 parts of the coppercomplex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid. A mixture of dyes which, in the form of the free acid, have theformulae (105) and (106), in which

F₁ is in each case as defined in Table 2,

A₁ is a radical of the formula (104)

and B₁ is a radical of the formula

 is obtained.

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLES 70 TO 77

A The procedure described in Example 1 is repeated, except that anequimolar amount of an azo dye A₁—NH₂, in which

A₁ is in each case as defined in Table 3,

is used in place of the 10.02 parts of4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acid. A mixtureof dyes which, in the form of the free acid, have the formulae (101) and(102), in which

F₁ is a radical of the formula (103),

A₁ is in each case as defined in Table 3,

and B₁ is a radical of the formula

 is obtained.

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

TABLE 3 Example A₁ 70

71

72

73

74

75

76

77

EXAMPLES 78 bis 85

The procedure described in Example 1 is repeated, except that anequimolar amount of a copper complex azo dye F₁—NH₂, in which F₁ is ineach case as defined in Table 4, is used in place of the 29.80 parts ofthe copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid. A mixture of dyes which, in the form of the free acid, have theformulae (101) and (102), in which

F₁ is in each case as defined in Table 4,

A₁ is a radical of the formula (104)

and B₁ is a radical of the formula

 is obtained.

TABLE 4 Example F₁ (Chromophor of the formula) 78 (I.1) 79 (I.2) 80(I.3) 81 (I.4) 82 (I.5) 83 (II.1) 84 (II.2)  84a (II.3) 85 (III.1)

EXAMPLES 86 TO 110

The procedure described in Example 1 is repeated, except that anequimolar amount of a diamine

in which the radical

is in each case as as defined in Table 5, is used in place of the 2.83parts of 1,2-diaminopropane. A mixture of dyes which, in the form of thefree acid, have the formulae (109) and (110)

in which

F₁ is a radical of the formula (103),

A₁ is a radical of the formula (104) and the radical

 is in each case as defined in Table 5

is obtained.

TABLE 5 Example

86 —NH—CH₂—CH₂—NH— 87 —NH—CH₂—CH₂—CH₂—NH— 88 —NH—CH₂—CH₂—N(CH₃)— 89—N(CH₃)—CH₂—CH₂—N(CH₃)— 90 —NH—(CH₂)₂—NH—(CH₂)₂—NH— 91—NH—(CH₂)₃—O—(CH₂)₄—O—(CH₂)₃—NH— 92 —NH—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—NH— 93—NH—CH₂—CH₂—N(CH₂CH₃)— 94

95

96

97

98

99

100

101

102

103

104

105

106

107

108

109

110

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLES 111 TO 141

The procedure described in Example 3 is repeated, except that anequimolar amount of a compound of the formula H-X, in which the radicalX is in each case as defined in Table 6, is used in place of the 1.92parts of morpholine. A mixture of dyes which, in the form of the freeacid, have the formulae (111) and (112)

in which

F₁ is a radical of the formula (103),

A₁ is a radical of the formula (104) and

B₁ is a radical of the formula

 and the radical X is in each case as defined in Table 6,

is obtained.

TABLE 6 Example X 111 —NH₂ 112 —N(CH₃)2 113 —NH—CH₂—CH₃ 114—NH—CH₂—CH₂—OH 115 —NH—CH₂—CH₂—O—CH₂—CH₂—OH 116

117 —N(CH₂—CH₂—OH)₂ 118 —NH—CH₂—CH₂—OSO₃H 119 —NH—CH₂—CH₂—SO₃H 120—N(CH₃)—CH₂—CH₂—SO₃H 121 —NH—CH₂—COOH 122 —NH—CH₂—CH₂—COOH 123—NH—CH₂—CH₂—CH₂— COOH 124 —N(CH₂—COOH)₂ 125

126

127

128

129

130

131

132

133

134

135

136

137

138 —S—CH₂—CH₂—COOH 139 —S—CH₂—COOH 140 —S—CH₂—CH₂—OH 141—S—CH₂—CH₂—CH₂—SO₃H

The dye mixtures give prints on paper and dyeings and prints on cottonand wool in black colour shades of high fastness to light.

EXAMPLE 142

a) 14 parts of cyanuric fluoride are added dropwise to a neutralsolution of 52 parts of4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acid and 5parts of disodium hydrogen phosphate in 500 parts of water at atemperature below 2° C., the pH being kept constant by on of sodiumhydroxide solution. When the reaction has ended 7.4 parts of1,2-diaminopropane in 54 parts of water are added dropwise such that thetemperature does not exceed 5° C. and the pH remains at a value of 6.The pH is then kept at a value of 6. A solution of4-{2-ureido-4-[4-(2-aminopropylamino)-6-fluoro-1,3,5-triazin-2-ylamino]phenylazo}-azobenzene-3,4′-disulfonicacid is obtained.

b) 14 parts of cyanuric fluoride are added dropwise to a neutralsolution of 60 parts of the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxy-benzenesulfonicacid and 5 parts of disodium hydrogen phosphate in 500 parts of at atemperature below 2° C., the pH being kept constant by addition ofsodium hydroxide solution. A solution of5-[4,6-difluoro-1,3,5-triazin-2-ylamino]-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]4-hydroxybenzenesulfonicacid is obtained.

c) The solution according to b) is added to the solution according toa), the pH being increased to and kept at a value of 8.5. The mixture isallowed to warm to room temperature, the solution is freed from the saltby dialysis and the dye is concentrated by evaporation. A dye which, inthe form of the free acid, is the compound of the formula (113)

in which

F₅ is a radical of the formula (103), A₄ is a radical of the formula(104) and

B₅ is a radical of the formula

 is obtained.

The dye dyes cotton and wool in olive colour shades of high fastness tolight.

EXAMPLE 143

19 parts of morpholine are added at 20° C. and a pH of 8.5 to a solutionobtained according to Example 142 c), which comprises the dye of theformula (113). The reaction mixture is heated to 50 to 55° C. and the pHis brought to 10 by addition of sodium hydroxide solution. The mixtureis stirred at this temperature for about a further one hour. Thereaction mixture is then allowed to cool to room temperature, and the pHis brought to 7 to 7.5 with aqueous hydrochloric acid. The resultingsolution is freed from the salt by dialysis and evaporated. A dye which,in the form of the free acid, has the formula (114)

in which

F₅ is a radical of the formula (103), A₄ is a radical of the formula(104) and

B₅ is a radical of the formula

 is obtained.

The dye dyes cotton and wool in olive colour shades of high fastness tolight.

The procedure described in Example 142 is repeated, except that anequimolar amount of a disazo dye A₁—NH₂, in which A₁ is a radical of theformula

and R₁, R₁′, R₂ and R₂′ are each as defined in Table 1, is used in placeof the 52 parts of4-(2-ureido-4-aminophenylazo)-azobenzene-3,4′-disulfonic acid. Valuabledyes which dye cotton and wool in olive colour shades of high fastnessto light are likewise obtained.

The procedure described in Example 142 is repeated, except that anequimolar amount of a formazan dye shown in Table 2 or of a coppercomplex azo dye shown in Table 4 is used in place of the 60 parts of thecopper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid. Valuable dyes which dye cotton and wool in olive colour shades ofhigh fastness to light are likewise obtained.

The procedure described in Example 142 is repeated, except that anequimolar amount of a diamine according to Table 5 is used in place ofthe 7.4 parts of 1,2-diaminopropane. Valuable dyes which dye cotton andwool in olive colour shades of high fastness to light are likewiseobtained.

The procedure described in Example 143 is repeated, except that anequimolar amount of a compound X—H, in which X is in each case asdefined in Table 6, is used in place of the 19 parts of morpholine.Valuable dyes which dye cotton and wool in olive colour shades of highfastness to light are likewise obtained.

EXAMPLE 144

a) 9.22 parts of cyanuric chloride are suspended in 150 parts ofice-water. The pH is brought to 5 with 1 N sodium hydroxide solution andthe temperature is kept at 0 to 2° C. A neutral solution of 29.80 partsof the copper complex of5-amino-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid in 250 parts of water is added to this suspension at 0 to 3° C.During the addition the pH is kept at 5 with a 2 N sodium hydroxidesolution. After the addition the mixture is stirred at 0 to 3° C. and pH5 for about a further 2 hours. A solution of5-[4,6-dichloro-1,3,5-triazin-2-ylamino]-3-[3-phenyl-5-(2-carboxy-5-sulfophenyl)-1-formazano]-4-hydroxybenzenesulfonicacid is obtained.

b) The solution obtained according to a) is added dropwise to asolution, brought to pH 6 to 6.5 with 32% hydrochloric acid, of 37.1parts of 1,2-diaminopropane in 50 parts of ice-water, the pH being keptat 6.5 by addition of a 15% sodium hydroxide solution. During thedropwise addition the temperature is allowed to rise to about 20° C. Tobring the reaction to completion the mixture is stirred at 30° C. for 2days. The crystalline product is then filtered off, washed with waterand taken up in 700 parts of water. Complete solution occurs byincreasing the pH to 9.5 with 15% sodium hydroxide solution. The dye isprecipitated again by addition of 90 parts of sodium chloride, filteredoff and washed with 15% sodium chloride solution. After drying at 50° C.in vacuo 54.8 parts of a compound which, in the form of the free acid,has the formula

in which B₄ is a radical of the formula

is obtained.

c) 10.96 parts of the compound according to b) are dissolved in 75 partsof water under neutral conditions and the pH is then brought to 8.8 with1 N sodium hydroxide solution. A neutral solution of 4.58 parts of acompound of the formula

(obtained by vinylation of C.I. Reactive Red 23 in an alkaline medium)in 50 parts of water is added dropwise to this solution at 50 to 55° C.,the pH being kept at 8.8 by addition of a 1N sodium hydroxide solution.To bring the reaction to completion the mixture is further stirred forsome hours. The solution is clarified by filtration, freed from the saltby dialysis and freeze-dried. 11.3 parts of a compound which, in theform of the free acid, has the formula (115)

in which B₄ is a radical of the formula

are obtained.

APPLICATION EXAMPLE 1

10.0 parts of the dye mixture according to Example 1 are dissolved in90.0 parts of distilled water and 10 parts of 1,2-propylene glycol andthe solution is filtered. The ink thus obtained is printed onto acommercially available ink-jet paper or photographic paper or a glossyfilm (for example Epson Glossy Film) by means of a drop-on-demandink-jet printer. The resulting print in a black shade has a very goodfastness to light.

The procedure described in application example 1 is repeated, exceptthat one of the dye mixtures according to Examples 2 to 141 is used inplace of the dye mixture according to Example 1. Black prints of verygood fastness to light are likewise obtained.

APPLICATION EXAMPLE 2

3.57 parts of a dye which, in the form of the free acid, has the formula(105)

in which F₁ is a radical of the formula (103)

and 1.20 parts of a dye which, in the form of the free acid, has theformula (116)

in which A₁ is a radical of the formula (104)

are dissolved in 40 parts of distilled water and 5.0 parts of1,2-propylene glycol and the solution is filtered. The ink thus obtainedis printed onto a commercially available ink-jet paper, photographicpaper or a glossy film (for example Epson Glossy Film) or onto cottonaccording to application example 5 by means of a drop-on-demand ink-jetprinter. The resulting print in a black shade has a very good fastnessto light.

APPLICATION EXAMPLE 3

3.78 parts of a dye of the formula (IV.8) and 1.20 parts of a dye of theformula (116), in which A₁ is a radical of the formula (104), aredissolved in a mixture of 35 parts of distilled water, 5 parts of1,2-propylene glycol and 5.0 parts of glycerol and the solution isfiltered. The ink thus obtained is printed onto a commercially availableink-jet paper or photographic paper or a glossy film (for example EpsonGlossy Film) by means of a drop-on-demand ink-jet printer. The resultingprint in a black shade has a very good fastness to light.

APPLICATION EXAMPLE 4

The following inks (a) to (m) are prepared by dissolving the compoundsstated in distilled water and the stated solvents. The inks are filteredand printed onto a commercially available ink-jet paper or photographicpaper or a glossy film (for example Epson Glossy Film) by means of adrop-on-demand ink-jet printer. The prints in a black shade obtainedwith the inks (a) to (m) have a very good fastness to light.

(a) 8.1 parts of a dye of the formula (IV.7); 1.8 parts of a dye of theformula (2.4); 10.0 parts of 1,2-propylene glycol; 10.0 parts ofglycerol and 70.1 parts of water.

(b) 9.2 parts of a dye of the formula (IV.2); 2.1 parts of a dye of theformula (2.7); 20.0 parts of 1,2-propylene glycol and 68.7 parts ofwater.

(c) 7.5 parts of a dye of the formula (IV.3); 2.3 parts of a dye of theformula (2.1); 20.0 parts of glycerol and 70.2 parts of water.

(d) 8.2 parts of a dye of the formula (IV.4); 1.9 parts of a dye of theformula (2.2); 0.2 parts of C.I. Reactive Red 23; 10.0 parts of1,2-propylene glycol; 5.0 parts of ε-caprolactam and 74.7 parts ofwater.

(e) 7.7 parts of a dye of the formula (IV.5); 2.5 parts of a dye of theformula (2.3); 0.1 part of C.I. Reactive Red 130; 10.0 parts of1,2-propylene glycol; 10.0 parts of glycerol; 5.0 parts ofN-methylpyrrolidone and 64.7 parts of water.

(f) 8.6 parts of a dye of the formula (IV.6); 2.7 parts of a dye of theformula (2.6); 20.0 parts of 1,2-propylene glycol and 68.7 parts ofwater.

(g) 9.0 parts of a dye of the formula (IV.9); 1.7 parts of a dye of theformula (2.5); 0.1 part of C.I. Reactive Red 23; 10.0 parts of1,2-propylene glycol; 10.0 parts of glycerol and 69.2 parts of water.

(h) 10.0 parts of the dye mixture according to Example 1; 0.1 part ofC.1. Reactive Red 23; 10.0 parts of 1,2-propylene glycol; 5.0 parts ofglycerol; 5.0 parts of ε-caprolactam and 69.9 parts of water.

(i) 9.2 parts of a dye of the formula (IV.3); 1.8 parts of a dye of theformula (2.6); 20.0 parts of 1,2-propylene glycol and 69.0 parts ofwater.

(j) 9.0 parts of the dye mixture according to Example 1; 1.0 part of thedye according to Example 144; 20.0 parts of 1,2-propylene glycol; 5.0parts of ε-caprolactam and 65.0 parts of water.

(k) 8.0 parts of a dye of the formula

2.0 parts of a dye of the formula (2.6); 20.0 parts of 1,2-propyleneglycol and 70.0 parts of water.

(l) 12.3 parts of a dye of the formula

2.3 parts of a dye of the formula (2.3); 20.0 parts of 1,2-propyleneglycol and 65.4 parts of water.

(m) II.0 parts of a dye of the formula

1.9 parts of a dye of the formula (2.2); 20.0 parts of 1,2-propyleneglycol and 67.1 parts of water.

APPLICATION EXAMPLE 5

a) Mercerized cotton-satin is added with a liquor comprising 30 g/l ofsodium carbonate (liquor pick-up 70%) and dried.

b) An aqueous ink with a viscosity of 2 mPa.s, comprising

15% by weight of the dye mixture according to Example 1,

15% by weight of 1,2-propylene glycol,

0.5% by weight of borax and

69.5% by weight of water,

is printed with a drop-on-demand ink-jet head (bubble jet) onto thecotton-satin pretreated according to step a). The print is driedcompletely, fixed in saturated steam for 4 minutes at 102° C., rinsed inthe cold, washed out at the boil, rinsed again and dried. A black printwith very good fastness to light is obtained.

The procedure described in application example 5 is repeated, exceptthat one of the dye mixtures according to Examples 2 to 141 is used inplace of the dye mixture according to Example 1. Black prints of verygood fastness to light are likewise obtained.

Dyeing instructions

2 parts of the dye obtained according to Example 142 are dissolved in400 parts of water; 1500 parts of a solution which comprises 53 g ofsodium chloride per litre are added to this. 100 parts of cotton fabricare introduced into this dyebath at 40° C. After 45 minutes 100 parts ofa solution which comprises 16 g of sodium hydroxide and 20 g of calcinedsodium carbonate per litre are added. The temperature of the dyebath iskept at 40° C. for a further 45 minutes. Thereafter, the dyed goods arerinsed, soaked at the boil with a nonionic detergent for a quarter of anhour, rinsed again and dried.

Printing instructions

3 parts of the dye obtained according to Example 142 are sprinkled, withrapid stirring, into 100 parts of a stock thickener comprising 50 partsof 5% sodium alginate thickener, 27.8 parts of water, 20 parts of urea,1 part of sodium m-nitrobenzenesulfonate and 1.2 parts of sodiumbicarbonate. A cotton fabric is printed with the printing paste thusobtained and dried and the resulting printed material is steamed insaturated steam for 2 minutes at 102° C. The printed fabric is thenrinsed, soaked at the boil, if appropriate, and rinsed again, and thendried.

What is claimed is:
 1. A black-dyeing aqueous ink comprising 20 to 95%by weight of at least one dye (A), together with 5 to 80% by weight ofat least one dye selected from the group consisting of (B) and (C),based on the total weight of the dyes (A), (B) and (C) in the ink, and 1to 40% by weight of a water-miscible organic solvent, based on the totalweight of the ink, the dye (A) containing, as the colouring part of themolecule, one or more radicals of the formula (I), (II), (III) or (IV)

 the dye (B) containing, as the colouring part of the molecule, one ormore mono- or disazo radicals containing sulfo groups or one or moreradicals of the formula (V), (VI), (VII) or (VIII)

 and the dye (C) containing, as the colouring part of the molecule, oneor more mono- or disazo radicals containing sulfo groups or one or moreradicals of the abovementioned formula (V), (VI), (VII) or (VIII) andone or more radicals of the abovementioned formula (I), (II), (III) or(IV), in which (G)₀₋₂ is 0 to 2 identical or different substituentsselected from the group consisting of substituted or unsubstitutedamino, hydroxyl and nitro, L is substituted or unsubstituted amino, R ishalogen, C₁-C₄alkyl, C₁-C₄alkoxy, C₂-C₄alkanoylamino, hydroxyl,carboxyl, nitro or cyano, (V)₀₋₂ is 0 to 2 identical or differentsubstituents selected from the group consisting of halogen, C₁-C₄alkyl,C₁-C₄alkoxy, β-sulfatoethylsulfonyl and sulfo, (W)₀₋₁ is an N-acylradical, n is the number 0, 1, 2 or 3, m is the number 1, 2 or 3 and rand q are the number 0 or
 1. 2. An ink according to claim 1, wherein thedye (A) contains, as the colouring part of the molecule, one or tworadicals of the formula (I), (II), (III) or (IV), the dye (B) contains,as the colouring part of the molecule, one or two mono- or disazoradicals containing sulfo groups or one or two radicals of the formula(V), (VI), (VII) or (VIII), and the dye (C) contains, as the colouringpart of the molecule, a mono- or disazo radical containing sulfo groupsor a radical of the formula (V), (VI), (VII) or (VIII) and a radical ofthe formula (I), (II), (III) or (IV).
 3. An ink according to claim 1,wherein the dye (A) has the formula (5)

 in which R₁₀, R₁₁, R₁₂ and R₁₃ independently of one another arehydrogen or substituted or unsubstituted C₁-C₄alkyl, B₁ is an aliphaticor aromatic bridge member, F₁ and F₂ independently of one another are aradical of the formula (I), (II), (III) or (IV), and X₁ and X₂independently of one another are halogen, hydroxyl, C₁-C₄alkoxy which isunsubstituted or substituted in the alkyl moiety, phenoxy which isunsubstituted or substituted in the phenyl ring, C₁-C₄alkylthio which isunsubstituted or substituted in the alkyl moiety, phenylthio which isunsubstituted or substituted in the phenyl ring, amino, N-mono- orN,N-di-C₁-C₆alkylamino which are unsubstituted or substituted in thealkyl moiety, C₅-C₇cycloalkylamino which is unsubstituted or substitutedin the cycloalkyl ring, phenyl- or naphthylamino orN-C₁-C₄alkyl-N-phenyl- or N-C₁-C₄alkyl-N-naphthylamino which areunsubstituted or substituted in the aryl moiety, benzylamino which isunsubstituted or substituted in the phenyl moiety, morpholino orpiperidin-1-yl.
 4. An ink according to claim 1, wherein the dye (B) hasthe formula (6)

and the dye (C has the formula (7)

 in which R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀ and R₂₁ independently of oneanother are hydrogen or substituted or unsubstituted C₁-C₄alkyl, B₂ andB₃ independently of one another are an aliphatic or aromatic bridgemember, A₁, A₂ and A₃ independently of one another are a mono- or disazoradical containing sulfo groups or a radical of the formula (V), (VI) or(VII), F₃ is a radical of the formula (I), (II), (III) or (IV) and X₃,X₄, X₅ and X₆ independently of one another are halogen, hydroxyl,C₁-C₄alkoxy which is unsubstituted or substituted in the alkyl moiety,phenoxy which is unsubstituted or substituted in the phenyl ring,C₁-C₄alkylthio which is unsubstituted or substituted in the alkylmoiety, phenylthio which is unsubstituted or substituted in the phenylring, amino, N-mono- or N,N-di-C₁-C₆alkylamino which are unsubstitutedor substituted in the alkyl moiety, C₅-C₇cycloalkylamino which isunsubstituted or substituted in the cycloalkyl ring, phenyl- ornaphthylamino or N-C₁-C₄alkyl-N-phenyl- or N-C₁-C₄alkyl-N-naphthylaminowhich are unsubstituted or substituted in the aryl moiety, benzylaminowhich is unsubstituted or substituted in the phenyl moiety, morpholinoor piperidin-1-yl.
 5. An ink according to claim 1, wherein the radicalof the formula (IV) in the dye (A) or (C) is a radical of the formula(IVa), (IVb) or (IVc)


6. An ink according to claim 1, wherein the mono- or disazo radicalscontaining sulfo groups in the dye (B) or (C) have the formula (4a),(4b), (4c), (4d), (4e), (4f), (4g), (4h), (4i), (4j), (4k), (41), (4m),(4n), (4o), (4p), (4q) or (4r)

in which (R₁)₀₋₃ is 0 to 3 identical or different substituents selectedfrom the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy,C₂-C₄alkanoylamino, halogen, carboxyl and sulfo and Z is vinyl or aradical —CH₂—CH₂—U and U is a leaving group,

in which (R₁)₀₋₃ is as defined above,

in which (R₁)₀₋₃ is as defined above,

in which (R₂)₀₋₄ is 0 to 4 identical or different substituents selectedfrom the group consisting of halogen, nitro, cyano, trifluoromethyl,sulfamoyl, carbamoyl, C₁-C₄alkyl, C₁-C₄alkoxy which is unsubstituted orsubstituted by hydroxyl or C₁-C₄alkoxy, amino, C₂-C₄alkanoylamino,ureido, hydroxyl, carboxyl, sulfomethyl, C₁-C₄alkylsulfonylamino andsulfo and Z is as defined above,

in which R₃ is C₂-C₄alkanoyl or benzoyl,

in which R₃ is as defined above,

in which (R₄)₀₋₃ is 0 to 3 identical or different substituents selectedfrom the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyland sulfo,

in which (R₄)₀₋₃ is as defined above,

in which R₅ and R₇ independently of one another are hydrogen, C₁-C₄alkylor phenyl, and R₆ is hydrogen, cyano, carbamoyl or sulfomethyl,

in which (R₈)₀₋₂ is 0 to 2 identical or different substituents selectedfrom the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyland sulfo; and Z is as defined above,

in which (R₉)₀₋₂ is 0 to 2 identical or different substituents selectedfrom the group consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyland sulfo; and Z is as defined above,

in which (R₁)₀₋₃, (R₂)₀₋₃, (R₄)₀₋₃ and Z are each as defined above and(R₁′)₀₋₃ is 0 to 3 identical or different substituents selected from thegroup consisting of C₁-C₄alkyl, C₁-C₄alkoxy, halogen, carboxyl andsulfo.
 7. A process for printing paper, films of plastic or textilefibre materials by the ink-jet printing process, which comprisesapplying an aqueous ink according to claim 1 to these materials by acontinuous ink-jet method or by a drop-on-demand method.